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Dicoordinate Au(I)–Ethylene Complexes as Hydroamination Catalysts
[Image: see text] A series of gold(I)–ethylene π-complexes containing a family of bulky phosphine ligands has been prepared. The use of these sterically congested ligands is crucial to stabilize the gold(I)–ethylene bond and prevent decomposition, boosting up their catalytic performance in the highl...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8981211/ https://www.ncbi.nlm.nih.gov/pubmed/35391904 http://dx.doi.org/10.1021/acscatal.1c05823 |
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author | Navarro, Miquel Alférez, Macarena G. de Sousa, Morgane Miranda-Pizarro, Juan Campos, Jesús |
author_facet | Navarro, Miquel Alférez, Macarena G. de Sousa, Morgane Miranda-Pizarro, Juan Campos, Jesús |
author_sort | Navarro, Miquel |
collection | PubMed |
description | [Image: see text] A series of gold(I)–ethylene π-complexes containing a family of bulky phosphine ligands has been prepared. The use of these sterically congested ligands is crucial to stabilize the gold(I)–ethylene bond and prevent decomposition, boosting up their catalytic performance in the highly underexplored hydroamination of ethylene. The precatalysts bearing the most sterically demanding phosphines showed the best results reaching full conversion to the hydroaminated products under notably mild conditions (1 bar of ethylene pressure at 60 °C). Kinetic analysis together with density functional theory calculations revealed that the assistance of a second molecule of the nucleophile as a proton shuttle is preferred even when using an extremely congested cavity-shaped Au(I) complex. In addition, we have measured a strong primary kinetic isotopic effect that is consistent with the involvement of X–H bond-breaking events in the protodeauration turnover-limiting step. |
format | Online Article Text |
id | pubmed-8981211 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-89812112022-04-05 Dicoordinate Au(I)–Ethylene Complexes as Hydroamination Catalysts Navarro, Miquel Alférez, Macarena G. de Sousa, Morgane Miranda-Pizarro, Juan Campos, Jesús ACS Catal [Image: see text] A series of gold(I)–ethylene π-complexes containing a family of bulky phosphine ligands has been prepared. The use of these sterically congested ligands is crucial to stabilize the gold(I)–ethylene bond and prevent decomposition, boosting up their catalytic performance in the highly underexplored hydroamination of ethylene. The precatalysts bearing the most sterically demanding phosphines showed the best results reaching full conversion to the hydroaminated products under notably mild conditions (1 bar of ethylene pressure at 60 °C). Kinetic analysis together with density functional theory calculations revealed that the assistance of a second molecule of the nucleophile as a proton shuttle is preferred even when using an extremely congested cavity-shaped Au(I) complex. In addition, we have measured a strong primary kinetic isotopic effect that is consistent with the involvement of X–H bond-breaking events in the protodeauration turnover-limiting step. American Chemical Society 2022-03-23 2022-04-01 /pmc/articles/PMC8981211/ /pubmed/35391904 http://dx.doi.org/10.1021/acscatal.1c05823 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Navarro, Miquel Alférez, Macarena G. de Sousa, Morgane Miranda-Pizarro, Juan Campos, Jesús Dicoordinate Au(I)–Ethylene Complexes as Hydroamination Catalysts |
title | Dicoordinate Au(I)–Ethylene Complexes as Hydroamination
Catalysts |
title_full | Dicoordinate Au(I)–Ethylene Complexes as Hydroamination
Catalysts |
title_fullStr | Dicoordinate Au(I)–Ethylene Complexes as Hydroamination
Catalysts |
title_full_unstemmed | Dicoordinate Au(I)–Ethylene Complexes as Hydroamination
Catalysts |
title_short | Dicoordinate Au(I)–Ethylene Complexes as Hydroamination
Catalysts |
title_sort | dicoordinate au(i)–ethylene complexes as hydroamination
catalysts |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8981211/ https://www.ncbi.nlm.nih.gov/pubmed/35391904 http://dx.doi.org/10.1021/acscatal.1c05823 |
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